US4026851A - Acrylate polymers cured with diamines in the presence of an acid catalyst - Google Patents
Acrylate polymers cured with diamines in the presence of an acid catalyst Download PDFInfo
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- US4026851A US4026851A US05/626,756 US62675675A US4026851A US 4026851 A US4026851 A US 4026851A US 62675675 A US62675675 A US 62675675A US 4026851 A US4026851 A US 4026851A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/005—Stabilisers against oxidation, heat, light, ozone
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
Definitions
- This invention relates to the curing of an acrylate, ethylene/acrylate, or ethylene/methacrylate/acrylate polymer with diamines in the presence of certain acid catalysts.
- Ethylene/acrylate or ethylene/methacrylate/acrylate polymers can be cured with free radical systems as described in U.S. Pat. No. 3,873,494, to K. J. Lewis.
- amine cures are preferred for acrylate-based polymers because they give vulcanizates with desirable properties such as low compression set, high tensile strength, and good heat aging.
- amine vulcanization of these polymers may not require the presence of a cure site monomer in the polymer and this is desirable in terms of economy and synthesis.
- This invention relates to a composition consisting essentially of about 100 parts by weight of a polymer containing at least 25 weight percent of a C 1 -C 4 alkyl acrylate (e.g., ethyl acrylate is a C 2 alkyl acrylate), about 0.5 to 10 parts by weight of at least one C 2 -C 12 diprimary amine, and about 0.5 to 10 parts by weight of at least one acid selected from C 4 -C 25 ⁇ -carbon atom branched aliphatic acids and aromatic acids whose pK A in aqueous solution is at least 3.0.
- a polymer containing at least 25 weight percent of a C 1 -C 4 alkyl acrylate (e.g., ethyl acrylate is a C 2 alkyl acrylate), about 0.5 to 10 parts by weight of at least one C 2 -C 12 diprimary amine, and about 0.5 to 10 parts by weight of at least one acid selected from C 4 -C 25 ⁇
- This invention relates to vulcanizing certain polymers with diamines in thepresence of certain acid catalysts.
- the polymers vulcanized according to this invention must contain at least 25 weight percent of a C 1 -C 4 alkyl acrylate. If less than this amount is present, poor vulcanization occurs due to insufficient crosslink sites, and the polymer will have poor oil and heat resistance.
- Polymers which contain at least 25weight percent of a C 1 -C 4 alkyl acrylate are well known in the art, e.g., Encyclopedia of Polymer Science and Technology, Vol. 1, page 271, Interscience Publishers, New York, N.Y. (1964).
- Such polymers can include C 1 -C 4 alkyl acrylate polymers, ethylene/C 1 -C 4 alkyl acrylate dipolymers, and ethylene/C 1 -C 4 alkyl methacrylate (e.g., ethyl methacrylate is a C 2 alkyl methacrylate)/C 1 -C 4 alkyl acrylate terpolymers.
- the polymer should have a molecular weight such that the melt index at 190° C. is about 0.1-70.
- the preferred range is about 0.5 and 15.
- the poly (alkyl acrylates) described in this invention can be prepared by emulsion polymerization as described in the Encyclopedia of Polymer Science and Technology, Vol. 1, page 270, Interscience Publishers, New York, N.Y., 1964.
- Alkyl acrylate monomers used to prepare such polymers are C 1 -C 4 alkyl acrylates and include: methyl acrylate, ethyl acrylate, propyl acrylates, and butyl acrylates.
- the ethylene/alkyl acrylate copolymers can be prepared by a high pressure polymerization process such as that described in U.S. Pat. No. 3,350,372, to H. T. Anspon, (column 1, lines 31 etc).
- Alkyl methacrylate polymers used in practicing this invention are prepared from C 1 -C 4 alkyl methacrylates and include: methyl methacrylate, ethyl methacrylate, propyl methacrylates, and butyl methacrylates.
- Diprimary amines useful in the compositions of this invention have the general formula NH 2 --R--NH 2 . These diprimary amines can containsecondary or tertiary nitrogen, ether oxygen, or sulfide sulfur without adverse results.
- Amines which can be used in the present invention include:
- amine-terminated polyethers containing up to 12 carbon atoms such as NH 2 CH 2 CH 2 OCH 2 CH 2 NH 2
- amine-terminated polysulfides containing up to 12 carbon atoms such as NH 2 (CH 2 CH 2 S) 2 CH 2 CH 2 NH 2
- preferred amines are hexamethylene diamine and diethylene triamine. These amines are preferred because they yield vulcanizates having the best tensile properties and they are readily available from commercial sources.
- the amount of amine required is about 0.5 to 10 parts per 100 parts of polymer. If less than about 0.5 part amine per 100 parts polymer is used, the degree of cure will be too low. More than about 10 parts per 100 partspolymer does not provide any further beneficial results. Mixtures of aminescan also be used.
- Acid catalysts used in this invention are C 4 -C 25 ⁇ -carbon atom branched aliphatic acids. Examples of these acids include:
- Aromatic acids whose pK A in aqueous solution is at least 3.0, can also be used as acid catalysts in compositions of this invention.
- the preferred acids for this invention include 2-ethylhexanoic, triethylacetic, pivalic, and benzoic.
- the amount of acid required is about 0.5 to 10 parts per 100 parts of polymer. If less than about 0.5 part of acid per 100 parts polymer is used, the acid will have too low a catalytic effect. If greater than about10 parts acid per 100 parts elastomer is used, no additional benefits are obtained.
- compositions of the present invention can contain an antioxidant of thephosphorus ester type, the hindered phenolic type, the amine type, or a mixture of two or more of these compounds.
- Phosphorus ester compounds which can be used include:
- Hindered phenolic compounds which can be used include:
- Amine antioxidants which can be used include:
- the preferred antioxidant is tri(mixed mono- and dinonylphenyl) phosphite in a mixture with either 4,4'-bis-( ⁇ , ⁇ -dimethylbenzyl)diphenylamine or 4,4'-butylidenebis (6-t-butyl-m-cresol).
- the weight ratio of the phenolic or amine antioxidant to the phosphorus compound in the mixtures is about 0.5-3, the preferred ratio being about 1.
- compositions of this invention containing an anti-oxidant produce good heat-aging vulcanizates.
- the amount of antioxidant compound in the vulcanizing composition is about 0.1-14 5 parts per 100 parts of polymer, the preferred proportion being about 0.5-2.5.
- the antioxidant effect is minor below the broad range recited above. Above the broad range, little additional improvement is observed, and there may be adverse effects on the state of cure.
- Fillers can be added to reduce cost and to improve the mechanical properties in a vulcanizate.
- a typical vulcanizable composition will usually contain about 15-40 percent by volume of fillers, depending on thereinforcing effect of the individual fillers. The preferred amount of fillers is about 20-25 percent by volume. If less than about 15 percent byvolume is used, the improvement of tensile properties is quite low, while if more than about 50 percent by volume is used, the processability of thepolymer may be adversely affected.
- Conventional fillers including carbon black, barium sulfate, magnesium silicate, and silica, can be used.
- the ingredients of the vulcanizable composition can be mixed in conventional equipment, such as a two-roll mill or a Banbury mixer.
- the vulcanizate may be formed and press-cured using conventional procedures atabout 170°-210° C. for about 15-60 minutes.
- copolymers were prepared by copolymerizing mixtures of ethylene and alkyl acrylate or methacrylate in the presence of a free-radical polymerization initiator in a pressure reactor at 125°-175° C. and a pressure of 1700-1900 atm.
- Thealkyl acrylates contained 530-1200 ppm of a stabilizer, the monomethyl ether of hydroquinone.
- the free-radical polymerization initiator used was t-butylperoxypivalate. Each polymerization was run as a continuous process, and ethylene, acrylate monomer, and benzene solvents were fed continuously into a 325 or 720 cc.
- Copolymers were vulcanized by the following procedure. On a 2-roll ruber mill, at about 50°-75° C., were mixed copolymer, carbon black, curing agent, antioxidants, and other additives as indicated. The compositions were sheeted off the mill and specimens for physical testing were prepared. Vulcanizate slabs, 0.075 in. thick, were prepared by press-curing for 30 minutes at 180° C. at about a total gage pressure of 40,000 lbs. Modulus, tensile strength, and elongation values were obtained at room temperature by ASTM Method D-412-66 on press-cured samples. Percent volume oil swell after immersion in ASTM #3 oil for 70 hrs. at 150° C.
- Oscillating Disc Rheometer ODR measurements were obtained on the uncured stocks by ASTM Method D-2705. The maximum cure rate was obtained by drawing a tangent at the steepest part of the rise ofthe curing curve on a plot of torque versus time and dividing the night of the tangent by the time required to transverse that night.
- This example illustrates that as the number of alkyl groups on the ⁇ -carbon of an ⁇ -carbon atom branched aliphatic acid increases, the cure rate and cure state increase.
- This example illustrates the vulcanization of an ethylene/methyl acrylate polymer using various ⁇ -alkyl-substituted acids and aromatic acids as accelerators.
- This example illustrates that a salt reaction product which results when anacid and an amine are reacted can be substituted for the acid and the diamine in the vulcanizate.
- This example illustrates that the branched acid catalysis is effective withvarious primary diamine curing agents.
- This example illustrates vulcanization of two other types of acrylate polymers.
- This example shows that a branched acid is a more effective catalyst than along chain fatty acid in vulcanizing compositions of this invention.
Abstract
A composition consisting essentially of A. A POLYMER HAVING AT LEAST 25 WEIGHT PERCENT OF C1-C4 alkyl acrylate units, B. A C2-C12 diprimary amine, and C. AT LEAST ONE ACID SELECTED FROM I. C4-C25 alpha-carbon branched aliphatic acids, and II. AROMATIC ACIDS WHOSE PKA in aqueous solution is at least 3.0.
Description
This application is a continuation-in-part of my copending application Ser. No. 605,711, filed Aug. 13, 1975, now abandoned.
This invention relates to the curing of an acrylate, ethylene/acrylate, or ethylene/methacrylate/acrylate polymer with diamines in the presence of certain acid catalysts.
Ethylene/acrylate or ethylene/methacrylate/acrylate polymers can be cured with free radical systems as described in U.S. Pat. No. 3,873,494, to K. J. Lewis. However, amine cures are preferred for acrylate-based polymers because they give vulcanizates with desirable properties such as low compression set, high tensile strength, and good heat aging. Also, amine vulcanization of these polymers may not require the presence of a cure site monomer in the polymer and this is desirable in terms of economy and synthesis.
U.S. Pat. No. 2,579,492, to J. E. Hansen and T. J. Dietz, describes the vulcanization of an acrylate-containing polymer with polymethylene or polyethylene diamines in the presence of a fatty acid which contains 8-18 carbon atoms. However, large amounts of the diamine are required and the rate of vulcanization is very slow. By employing the methods of the present invention, it is now possible to vulcanize acrylate, ethylene/acrylate, or ethylene/methacrylate/acrylate polymers with diamines at a much more rapid rate and with the use of smaller quantities of diamine.
This invention relates to a composition consisting essentially of about 100 parts by weight of a polymer containing at least 25 weight percent of a C1 -C4 alkyl acrylate (e.g., ethyl acrylate is a C2 alkyl acrylate), about 0.5 to 10 parts by weight of at least one C2 -C12 diprimary amine, and about 0.5 to 10 parts by weight of at least one acid selected from C4 -C25 α-carbon atom branched aliphatic acids and aromatic acids whose pKA in aqueous solution is at least 3.0.
This invention relates to vulcanizing certain polymers with diamines in thepresence of certain acid catalysts. The polymers vulcanized according to this invention must contain at least 25 weight percent of a C1 -C4 alkyl acrylate. If less than this amount is present, poor vulcanization occurs due to insufficient crosslink sites, and the polymer will have poor oil and heat resistance. Polymers which contain at least 25weight percent of a C1 -C4 alkyl acrylate are well known in the art, e.g., Encyclopedia of Polymer Science and Technology, Vol. 1, page 271, Interscience Publishers, New York, N.Y. (1964). Such polymers can include C1 -C4 alkyl acrylate polymers, ethylene/C1 -C4 alkyl acrylate dipolymers, and ethylene/C1 -C4 alkyl methacrylate (e.g., ethyl methacrylate is a C2 alkyl methacrylate)/C1 -C4 alkyl acrylate terpolymers.
The polymer should have a molecular weight such that the melt index at 190° C. is about 0.1-70. The preferred range is about 0.5 and 15.
The poly (alkyl acrylates) described in this invention can be prepared by emulsion polymerization as described in the Encyclopedia of Polymer Science and Technology, Vol. 1, page 270, Interscience Publishers, New York, N.Y., 1964. Alkyl acrylate monomers used to prepare such polymers are C1 -C4 alkyl acrylates and include: methyl acrylate, ethyl acrylate, propyl acrylates, and butyl acrylates.
The ethylene/alkyl acrylate copolymers can be prepared by a high pressure polymerization process such as that described in U.S. Pat. No. 3,350,372, to H. T. Anspon, (column 1, lines 31 etc).
Alkyl methacrylate polymers used in practicing this invention are prepared from C1 -C4 alkyl methacrylates and include: methyl methacrylate, ethyl methacrylate, propyl methacrylates, and butyl methacrylates.
Diprimary amines useful in the compositions of this invention have the general formula NH2 --R--NH2. These diprimary amines can containsecondary or tertiary nitrogen, ether oxygen, or sulfide sulfur without adverse results. Amines which can be used in the present invention include:
hexamethylene diamine
ethylene diamine
diethylene triamine
triethylene tetramine
xylylene diamine
1,4-butylene diamine
1,12-dodecyl diamine
amine-terminated polyethers containing up to 12 carbon atoms, such as NH2 CH2 CH2 OCH2 CH2 NH2
amine-terminated polysulfides containing up to 12 carbon atoms, such as NH2 (CH2 CH2 S)2 CH2 CH2 NH2
preferred amines are hexamethylene diamine and diethylene triamine. These amines are preferred because they yield vulcanizates having the best tensile properties and they are readily available from commercial sources.
The amount of amine required is about 0.5 to 10 parts per 100 parts of polymer. If less than about 0.5 part amine per 100 parts polymer is used, the degree of cure will be too low. More than about 10 parts per 100 partspolymer does not provide any further beneficial results. Mixtures of aminescan also be used.
Acid catalysts used in this invention are C4 -C25 α-carbon atom branched aliphatic acids. Examples of these acids include:
2-methyl propionic acid
2-ethylbutyric acid
triethylacetic acid
pivalic acid
2-ethylhexanoic acid
2,5-dimethyladipic acid
5-norbornene-2-carboxylic acid
bicyclo[2.2.2]octane-2-carboxylic acid
cyclohexanecarboxylic acid
methylmalonic acid
2-ethylglutaric acid
α-mono- and di branched valeric, caproic, stearic, lauric, and myristic acids
Aromatic acids, whose pKA in aqueous solution is at least 3.0, can also be used as acid catalysts in compositions of this invention.
Examples of these acids include:
benzoic acid
p-anisic acid
m-, or p-hydroxybenzoic acid
m-, or-p-bromobenzoic acid
m-, or p-chlorobenzoic acid
m-, or p-toluic acid
The preferred acids for this invention include 2-ethylhexanoic, triethylacetic, pivalic, and benzoic.
The amount of acid required is about 0.5 to 10 parts per 100 parts of polymer. If less than about 0.5 part of acid per 100 parts polymer is used, the acid will have too low a catalytic effect. If greater than about10 parts acid per 100 parts elastomer is used, no additional benefits are obtained.
The compositions of the present invention can contain an antioxidant of thephosphorus ester type, the hindered phenolic type, the amine type, or a mixture of two or more of these compounds.
Phosphorus ester compounds which can be used include:
tri (mixed mono- and dinonylphenyl) phosphite
tris (3,5-di-t-butyl-4-hydroxyphenyl) phosphate
high molecular weight poly (phenolic phosphonates), and
6-(3,5-di-t-butyl-4-hydroxy) benzyl-6H-dibenz[c, e] [1,2]oxaphosphorin-6-oxide
Hindered phenolic compounds which can be used include:
4,4-butylidenebis(6-t-butyl-m-cresol)
1,3,5-trimethyl-2,4,6-tris-(3,5-di-t-butyl-4-hydroxy benzyl)benzene
2,6-di-t-butyl-α-dimethylamino-p-cresol, and
4,4'-thiobis(3-methyl-6-t-butylphenol)
Amine antioxidants which can be used include:
polymerized 2,2,4-trimethyl-1,2-dihydroquinoline
N-phenyl-N'-(p-toluenesulfonyl)-p-phenylenediamine
N,n'-di(β-naphthyl)-p-phenylenediamine
low temperature reaction product of phenyl (β-naphthyl)amine and acetone
4,4'-bis-(α,α-dimethylbenzyl)diphenylamine
The preferred antioxidant is tri(mixed mono- and dinonylphenyl) phosphite in a mixture with either 4,4'-bis-(α,α-dimethylbenzyl)diphenylamine or 4,4'-butylidenebis (6-t-butyl-m-cresol). The weight ratio of the phenolic or amine antioxidant to the phosphorus compound in the mixtures is about 0.5-3, the preferred ratio being about 1.
Compositions of this invention containing an anti-oxidant produce good heat-aging vulcanizates. The amount of antioxidant compound in the vulcanizing composition is about 0.1-14 5 parts per 100 parts of polymer, the preferred proportion being about 0.5-2.5. The antioxidant effect is minor below the broad range recited above. Above the broad range, little additional improvement is observed, and there may be adverse effects on the state of cure.
Fillers can be added to reduce cost and to improve the mechanical properties in a vulcanizate. A typical vulcanizable composition will usually contain about 15-40 percent by volume of fillers, depending on thereinforcing effect of the individual fillers. The preferred amount of fillers is about 20-25 percent by volume. If less than about 15 percent byvolume is used, the improvement of tensile properties is quite low, while if more than about 50 percent by volume is used, the processability of thepolymer may be adversely affected. Conventional fillers, including carbon black, barium sulfate, magnesium silicate, and silica, can be used.
The ingredients of the vulcanizable composition can be mixed in conventional equipment, such as a two-roll mill or a Banbury mixer. The vulcanizate may be formed and press-cured using conventional procedures atabout 170°-210° C. for about 15-60 minutes.
The following examples illustrate this invention. All parts, percentages, and proportions are by weight unless otherwise specified.
In each of the following examples, copolymers were prepared by copolymerizing mixtures of ethylene and alkyl acrylate or methacrylate in the presence of a free-radical polymerization initiator in a pressure reactor at 125°-175° C. and a pressure of 1700-1900 atm. Thealkyl acrylates contained 530-1200 ppm of a stabilizer, the monomethyl ether of hydroquinone. The free-radical polymerization initiator used was t-butylperoxypivalate. Each polymerization was run as a continuous process, and ethylene, acrylate monomer, and benzene solvents were fed continuously into a 325 or 720 cc. stirred autoclave at rates of 7-18 lbs./hr., 0.4-1.5 lbs./hr., and 1.1-2.5 lbs./hr., respectively. Initiator was introduced continuously at a rate of about 1.0-5.5 lbs./1000 lbs. of polymer. The reaction mixture was continuously removed from the autoclave and was stripped of unpolymerized monomers and solvent under reduced pressure and at elevated temperature.
Melt indices of the resulting polymers were determined at 190° C. asdescribed in tentative ASTM Test Method D-1238-52T (ASTM Standards, 1955, Part 6, pages 292-295).
Copolymers were vulcanized by the following procedure. On a 2-roll ruber mill, at about 50°-75° C., were mixed copolymer, carbon black, curing agent, antioxidants, and other additives as indicated. The compositions were sheeted off the mill and specimens for physical testing were prepared. Vulcanizate slabs, 0.075 in. thick, were prepared by press-curing for 30 minutes at 180° C. at about a total gage pressure of 40,000 lbs. Modulus, tensile strength, and elongation values were obtained at room temperature by ASTM Method D-412-66 on press-cured samples. Percent volume oil swell after immersion in ASTM #3 oil for 70 hrs. at 150° C. was determined according to ASTM D-471-68 on press-cured samples. Oscillating Disc Rheometer (ODR) measurements were obtained on the uncured stocks by ASTM Method D-2705. The maximum cure rate was obtained by drawing a tangent at the steepest part of the rise ofthe curing curve on a plot of torque versus time and dividing the night of the tangent by the time required to transverse that night.
This example illustrates that as the number of alkyl groups on the α-carbon of an α-carbon atom branched aliphatic acid increases, the cure rate and cure state increase.
______________________________________
Masterbatch Parts
Ethylene (47 wt.%)/methyl acrylate
100
(53%) copolymer.sup.a)
FEF carbon black 50
Tri(nonylated phenyl)phosphite.sup.b)
1
4,4'-Bis(α,α-dimethylbenzyl)diphenylamine
1
Aqueous 88% hexamethylene diamine
1.5
Masterbatch (parts)
153.5 153.5 153.5
Acid Propionic 2-Ethylbutyric
Triethylacetic
Parts 3.0 3.0 3.7
ODR at 180° C.
Maximum rate 0.06 2.3 2.9
Tensile Properties.sup.c)
M.sub.100 (psi)
200 575 650
T.sub.B (psi)
550 2525 2650
E.sub.B (%) 960 340 285
Permanent set (%)
171 9 4.5
Oil Swell.sup.c)
235 77 70
______________________________________
.sup.a) Melt index 1.7
.sup.b) Sold as "Polygard" by Naugatuck
.sup.c) After press-curing at 180° C. for 30 min.?
This example illustrates the vulcanization of an ethylene/methyl acrylate polymer using various α-alkyl-substituted acids and aromatic acids as accelerators.
______________________________________
Maximum
ODR at 200° C.
Vulcanization
Torque
Acid Rate.sup.a)
after 30 min.
______________________________________
None 1.2 5
Pivalic acid 6.6 120
2-Ethylhexanoic acid
7.5 126
5-Norbornene-2-carboxylic acid
6.2 99
2-Ethylbutyric acid
10.0 132
2,5-Dimethyladipic acid
5.4 100
Benzoic acid 5.4 100
p-Anisic acid 5.9 105
______________________________________
.sup.a) Vulcanizable compositions contained: 100 parts ethylene (47
wt.%)/methyl acrylate (53 wt.%) polymer, 50 FEF carbon black, 1
tri(nonylated phenyl)phosphite (sold as "Polygard" by Naugatuck), 1
4,4'-bis(α,α-dimethylbenzyl)diphenylamine, 4 aqueous 88%
hexamethylene diamine, 15-20 mmoles of the indicated acid.
This example illustrates that a salt reaction product which results when anacid and an amine are reacted can be substituted for the acid and the diamine in the vulcanizate.
______________________________________
Masterbatch (parts) Parts
Ethylene (47 wt.%)/methyl
100
acrylate (53) copolymer.sup.a)
FEF black 50
Tri(nonylated phenyl)phosphite
1
4,4'-Bis(α,α-dimethylbenzyl) di-
1
phenyl amine
Samples A B C
______________________________________
Masterbatch (parts)
152 152 152
Salt product of hexa-
4 -- --
methylene diamine/di-
pivalic acid reaction
Salt product of Hexa-
-- 5 --
methylene diamine/di-
2-ethylhexanoic acid
reaction
88% Aqueous hexamethyl-
-- -- 1.5
ene diamine
2-Ethylhexanoic acid
-- -- 6
ODR at 180° C.
Maximum rate 2.4 2.5 2.5
Tensile Properties.sup.b)
M.sub.100 (psi)
550 500 525
T.sub.B (psi) 2375 2425 2425
E.sub.B (%) 365 395 365
Permanent set (%)
10 11 10
Oil Swell.sup.b)
84 80 78
______________________________________
.sup.a) Melt index 1.7
.sup.b) After curing 30 min. at 180° C.
This example illustrates that the branched acid catalysis is effective withvarious primary diamine curing agents.
______________________________________
Masterbatch Parts
Ethylene (47 wt. %)/methyl
100
acrylate (53) copolymer.sup.a)
FEF Carbon black 50
Tri(nonylated phenyl)phosphite
1
4,4'-Bis(α,α-dimethylbenzyl)di-
1
phenylamine
Sample A B C D
______________________________________
Masterbatch
(parts) 152 152 152 152
Amine
Aq. 88% hex-
amethylene
diamine 4.0 -- -- --
Ethylene
diamine -- 2.0 -- --
Diethylene
triamine -- -- 3.6 --
Triethylene
tetramine
-- -- -- 5.0
2-Ethylbutl-
ic acid 3.0 3.0 3.0 3.0
ODR
at 180° C.
Maximum
rate 3.4 4.2 1.8 2.0
Oil Swell.sup.b)
55 47 36 34
Tensile
Properties.sup.b)
M.sub.100 (psi)
675 750 1450 950
T.sub.B (psi)
2050 2000 2000 1925
E.sub.B (%)
235 200 170 185
Permanent
set (%) 3 3 3 3
______________________________________
.sup.a) Melt index 1.7
.sup.b) After press-curing 30 min. at 180° C.
This example illustrates vulcanization of two other types of acrylate polymers.
______________________________________
Sample A B
______________________________________
Polymer 1.sup.a) 100 --
Polymer 2.sup.b) -- 100
FEF Black 50 50
Tri(nonylated phenyl)phosphite
1.0 1.25
4,4'-Bis(α,α-dimethylbenzyl)di-
1.0 1.25
phenyl amine
88% Aqueous hexamethylene diamine
4.0 --
2-Ethylhexanoic acid 3.2 --
Hexamethylene diamine/di-2-ethyl-
-- 5
hexanoic acid salt
ODR at 180° C.
Maximum rate 3.3 2.7
Tensile Properties.sup.c)
M.sub.100 (psi) -- 325
T.sub.B (psi) 1575 1650
E.sub.B (%) 80 505
Permanent set (%) 2 27
Oil Swell.sup.c) 6.5 121
______________________________________
.sup.a) Poly(ethyl acrylate) prepared by solution polymerization of ethyl
acrylate in benzene at 60° C. using azobisisobutyronitrile catalys
.sup.b) Ethylene (42 wt. %)/methyl acrylate (40)/methyl methacrylate (18)
terpolymer of melt index 13.
.sup.c) After curing 30 min. at 180° C.
This example shows that a branched acid is a more effective catalyst than along chain fatty acid in vulcanizing compositions of this invention.
______________________________________
Masterbatch Parts
______________________________________
Ethylene (47 wt. %)/methyl acrylate
100
(53) copolymer.sup.a)
FEF Carbon black 50
Tri(nonylated phenyl)phosphite
1
4,4'-Bis(α,α-dimethylbenzyl)diphenylamine
1
Sample A B C D
______________________________________
Masterbatch
(parts) 152 152 152 152
Aq. 88% hex-
amethylene-
1.5 1.5 -- --
diamine
Triethylene
tetramine
-- -- 4 4
2-Ethylbutyric
acid (moles)
0.034 -- 0.024 --
Stearic acid
(moles) -- 0.035 -- 0.021
ODR at
180° C.
Maximum
rate 1.9 0.11 3.8 1.4
Oil Swell.sup.b)
76.7 196.4 51.1 83.4
Tensile
Properties.sup.b)
M.sub.100 (psi)
775 180 900 500
T.sub.B (psi)
1950 825 2025 2000
E.sub.B (%)
250 850 200 430
Permanent
Set (%) 5.5 121 4 21
______________________________________
.sup.a) Melt index 1.7
hu b)After press-curing 30 min. at 180° C.
Claims (14)
1. A composition consisting essentially of:
(a) about 100 parts by weight of an acrylate, ethylene/acrylate or ethylene/methacrylate/acrylate polymer containing at least 25 weight percent of C1 -C4 alkyl acrylate units,
(b) about 0.5-10 parts by weight of at least one C2 -C12 diprimary amine, and
(c) about 0.5-10 parts by weight of at least one acid selected from
(i) C4 -C25 α-carbon atom branched aliphatic acids, and
(ii) aromatic acids whose pKA in aqueous solution is at least 3.0.
2. The composition of claim 1 in which the amine is selected from hexamethylene diamine and diethylene triamine.
3. The composition of claim 1 in which the acid is selected from 2-ethylhexanoic, triethylacetic, pivalic, and benzoic acid.
4. The composition of claim 2 in which the acid is selected from 2-ethylhexanoic, triethylacetic, pivalic, and benzoic acid.
5. The composition of claim 1 in which the polymer contains up to 75 weight percent ethylene units.
6. The composition of claim 5 in which the amine is selected from hexamethylene diamine and diethylene triamine.
7. The composition of claim 5 in which the acid is selected from 2-ethylhexanoic, triethylacetic, pivalic, and benzoic acid.
8. The composition of claim 6 in which the acid is selected from 2-ethylhexanoic, triethylacetic, pivalic, and benzoic acid.
9. The composition of claim 1 in which the polymer contains ethylene units, C1 -C4 alkyl methacrylate units, and C1 -C4 alkyl acrylate units.
10. The composition of claim 9 in which the amine is selected from hexamethylene diamine and diethylene triamine, and the acid is selected from 2-ethylhexanoic, triethylacetic, pivalic, and benzoic acid.
11. The composition of claim 9 in which the alkyl acrylate is selected from methyl acrylate, ethyl acrylate, propyl acrylates, and butyl acrylates, and the alkyl methacrylate is selected from methyl methacrylate, ethyl methacrylate, propyl methacrylates, and butyl methacrylates.
12. A cured composition obtained by curing at a temperature of about 170°-210° C. for about 15 to 60 minutes a composition consisting essentially of
(a) about 100 parts by weight of an acrylate, ethylene/acrylate or ethylene/methacrylate/acrylate polymer containing at least 25 weight percent of C1 -C4 alkyl acrylate units,
(b) about 0.5-10 part by weight of at least one C2 -C12 diprimary amine, and
(c) about 0.5-10 parts by weight of at least one acid selected from
(i) C4 -C25 α-carbon atom branched aliphatic acids, and
(ii) aromatic acids whose pKA in aqueous solution is at least 3.0.
13. The cured composition of claim 12 in which the polymer contains up to 75 weight percent ethylene units.
14. The cured composition of claim 12 in which the polymer contains ethylene units, C1 -C4 alkyl methacrylate units, and C1 -C4 alkyl acrylate units.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US05/626,756 US4026851A (en) | 1975-08-13 | 1975-10-29 | Acrylate polymers cured with diamines in the presence of an acid catalyst |
| JP51095012A JPS5946272B2 (en) | 1975-08-13 | 1976-08-11 | Acrylate polymer compositions and cured compositions |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US60571175A | 1975-08-13 | 1975-08-13 | |
| US05/626,756 US4026851A (en) | 1975-08-13 | 1975-10-29 | Acrylate polymers cured with diamines in the presence of an acid catalyst |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US60571175A Continuation-In-Part | 1975-08-13 | 1975-08-13 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US4026851A true US4026851A (en) | 1977-05-31 |
Family
ID=27085030
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US05/626,756 Expired - Lifetime US4026851A (en) | 1975-08-13 | 1975-10-29 | Acrylate polymers cured with diamines in the presence of an acid catalyst |
Country Status (2)
| Country | Link |
|---|---|
| US (1) | US4026851A (en) |
| JP (1) | JPS5946272B2 (en) |
Cited By (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4147741A (en) * | 1976-01-27 | 1979-04-03 | Standard Oil Company (Indiana) | Anti-drip additive system for fire retardant polypropylene |
| US4381378A (en) * | 1981-12-28 | 1983-04-26 | E. I. Du Pont De Nemours And Company | Method for vulcanizing ethylene/acrylic or vinyl ester/glycidyl(meth)acrylate copolymer with piperazinium dicarboxylate salt and composition for same |
| US4399263A (en) * | 1981-12-24 | 1983-08-16 | E. I. Du Pont De Nemours & Co. | Modification of ethylene/acrylate/carboxylic polymer |
| US4412043A (en) * | 1982-05-03 | 1983-10-25 | E. I. Du Pont De Nemours And Company | Vulcanizable ethylene copolymers |
| US4754056A (en) * | 1985-04-05 | 1988-06-28 | Desoto, Inc. | Radiation-curable coatings containing reactive pigment dispersants |
| DE3819336A1 (en) * | 1987-06-16 | 1988-12-29 | Denki Kagaku Kogyo Kk | ACRYLIC RUBBER MATERIAL |
| US5254627A (en) * | 1993-01-07 | 1993-10-19 | Ford Motor Company | Electrically conductive polypyrroleamine polymer networks |
| US5274046A (en) * | 1993-01-07 | 1993-12-28 | Ford Motor Company | Electrically conductive polypyrrolecarbonyl polymer networks |
| US5276102A (en) * | 1993-01-07 | 1994-01-04 | Ford Motor Company | Electrically conductive polythiopheneamine polymer networks |
| US5298327A (en) * | 1986-07-08 | 1994-03-29 | Lumenyte International Corporation | High temperature plastic light conduit and composition of matter therefor |
| US5328961A (en) * | 1993-01-07 | 1994-07-12 | Ford Motor Company | Electrically conductive polythiophenecarbonyl polymer networks |
| US5579429A (en) * | 1995-09-06 | 1996-11-26 | Dn Labs, Inc. | Laser dye doped fluorescent optical fiber and method of preparation of the same |
| WO1998008897A1 (en) * | 1996-08-30 | 1998-03-05 | Societe De Conseils De Recherches Et D'applications Scientifiques (S.C.R.A.S.) | Polycarboxylic based cross-linked copolymers |
| US6057014A (en) * | 1995-07-26 | 2000-05-02 | E. I. Du Pont De Nemours And Company | Laminates of composition for improving adhesion of elastomers to polymer compositions |
| US6229009B1 (en) | 1997-08-29 | 2001-05-08 | Societe De Conseils De Recherches Et D'applications Scientifiques (S.C.R.A.S.) | Polycarboxylic based cross-linked copolymers |
| US20030204025A1 (en) * | 2002-04-29 | 2003-10-30 | Mcbride Edward | Method of manufacturing cured ethylene acrylic and polyacrylate elastomers |
| US20080038362A1 (en) * | 2003-06-12 | 2008-02-14 | Won-Bong Park | Composition For An Enteric Coating Of Natural Product Containing Lectin |
| US8722154B2 (en) | 2008-09-22 | 2014-05-13 | Commonwealth Scientific And Industrial Research Organisation | Composition and method for preparation of electro-conductive polymer surfaces |
| EP2918608A1 (en) | 2014-03-10 | 2015-09-16 | LANXESS Deutschland GmbH | Hydrogenated nitrile rubber containing amino methyl group and method for producing the same |
| EP2918609A1 (en) | 2014-03-10 | 2015-09-16 | LANXESS Deutschland GmbH | Hydrogenated nitrile rubber containing amino methyl groups containing vulcanisable compositions , process for their vulcanization and vulcanisates obtainable by this process |
| EP2918612A1 (en) | 2014-03-10 | 2015-09-16 | LANXESS Deutschland GmbH | Hydrogenated nitrile rubber containing aminomethyl groups, method for producing the same, vulcanizable compositions containing hydrogenated nitrile rubber containing aminomethyl groups, method for their vulcanization and vulcanizates obtainable by this method |
| WO2016174203A1 (en) | 2015-04-30 | 2016-11-03 | Arlanxeo Deutschland Gmbh | Use of acrylate rubbers having improved low-temperature properties and good oil resistance for producing vulcanizable mixtures and vulcanized products |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2579492A (en) * | 1949-07-19 | 1951-12-25 | John E Hansen | Vulcanization of polymerized acrylic esters |
| US3445413A (en) * | 1967-11-14 | 1969-05-20 | Goodrich Co B F | Nitrogen-containing acrylic elastomers stabilized with inorganic phosphites |
-
1975
- 1975-10-29 US US05/626,756 patent/US4026851A/en not_active Expired - Lifetime
-
1976
- 1976-08-11 JP JP51095012A patent/JPS5946272B2/en not_active Expired
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2579492A (en) * | 1949-07-19 | 1951-12-25 | John E Hansen | Vulcanization of polymerized acrylic esters |
| US3445413A (en) * | 1967-11-14 | 1969-05-20 | Goodrich Co B F | Nitrogen-containing acrylic elastomers stabilized with inorganic phosphites |
Cited By (27)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4147741A (en) * | 1976-01-27 | 1979-04-03 | Standard Oil Company (Indiana) | Anti-drip additive system for fire retardant polypropylene |
| US4399263A (en) * | 1981-12-24 | 1983-08-16 | E. I. Du Pont De Nemours & Co. | Modification of ethylene/acrylate/carboxylic polymer |
| US4381378A (en) * | 1981-12-28 | 1983-04-26 | E. I. Du Pont De Nemours And Company | Method for vulcanizing ethylene/acrylic or vinyl ester/glycidyl(meth)acrylate copolymer with piperazinium dicarboxylate salt and composition for same |
| US4412043A (en) * | 1982-05-03 | 1983-10-25 | E. I. Du Pont De Nemours And Company | Vulcanizable ethylene copolymers |
| US4754056A (en) * | 1985-04-05 | 1988-06-28 | Desoto, Inc. | Radiation-curable coatings containing reactive pigment dispersants |
| US5298327A (en) * | 1986-07-08 | 1994-03-29 | Lumenyte International Corporation | High temperature plastic light conduit and composition of matter therefor |
| DE3819336C2 (en) * | 1987-06-16 | 1998-04-30 | Denki Kagaku Kogyo Kk | Acrylic rubber mass |
| DE3819336A1 (en) * | 1987-06-16 | 1988-12-29 | Denki Kagaku Kogyo Kk | ACRYLIC RUBBER MATERIAL |
| US5254627A (en) * | 1993-01-07 | 1993-10-19 | Ford Motor Company | Electrically conductive polypyrroleamine polymer networks |
| US5274046A (en) * | 1993-01-07 | 1993-12-28 | Ford Motor Company | Electrically conductive polypyrrolecarbonyl polymer networks |
| US5276102A (en) * | 1993-01-07 | 1994-01-04 | Ford Motor Company | Electrically conductive polythiopheneamine polymer networks |
| US5328961A (en) * | 1993-01-07 | 1994-07-12 | Ford Motor Company | Electrically conductive polythiophenecarbonyl polymer networks |
| US6057014A (en) * | 1995-07-26 | 2000-05-02 | E. I. Du Pont De Nemours And Company | Laminates of composition for improving adhesion of elastomers to polymer compositions |
| US5579429A (en) * | 1995-09-06 | 1996-11-26 | Dn Labs, Inc. | Laser dye doped fluorescent optical fiber and method of preparation of the same |
| WO1998008897A1 (en) * | 1996-08-30 | 1998-03-05 | Societe De Conseils De Recherches Et D'applications Scientifiques (S.C.R.A.S.) | Polycarboxylic based cross-linked copolymers |
| FR2752843A1 (en) * | 1996-08-30 | 1998-03-06 | Sod Conseils Rech Applic | CROSS-LINKED COPOLYMERS BASED ON POLYCARBOXYLIC POLYMERS AND THEIR USE AS A PHARMACEUTICAL COMPOSITION SUPPORT |
| US6229009B1 (en) | 1997-08-29 | 2001-05-08 | Societe De Conseils De Recherches Et D'applications Scientifiques (S.C.R.A.S.) | Polycarboxylic based cross-linked copolymers |
| US20030204025A1 (en) * | 2002-04-29 | 2003-10-30 | Mcbride Edward | Method of manufacturing cured ethylene acrylic and polyacrylate elastomers |
| WO2004041920A2 (en) * | 2002-04-29 | 2004-05-21 | E.I. Du Pont De Nemours And Company | Method of manufacturing cured ethylene acrylic and polyacrylate elastomers |
| WO2004041920A3 (en) * | 2002-04-29 | 2004-10-21 | Du Pont | Method of manufacturing cured ethylene acrylic and polyacrylate elastomers |
| US7001957B2 (en) | 2002-04-29 | 2006-02-21 | E.I. Du Pont De Nemours And Company, Inc. | Method of manufacturing cured ethylene acrylic and polyacrylate elastomers |
| US20080038362A1 (en) * | 2003-06-12 | 2008-02-14 | Won-Bong Park | Composition For An Enteric Coating Of Natural Product Containing Lectin |
| US8722154B2 (en) | 2008-09-22 | 2014-05-13 | Commonwealth Scientific And Industrial Research Organisation | Composition and method for preparation of electro-conductive polymer surfaces |
| EP2918608A1 (en) | 2014-03-10 | 2015-09-16 | LANXESS Deutschland GmbH | Hydrogenated nitrile rubber containing amino methyl group and method for producing the same |
| EP2918609A1 (en) | 2014-03-10 | 2015-09-16 | LANXESS Deutschland GmbH | Hydrogenated nitrile rubber containing amino methyl groups containing vulcanisable compositions , process for their vulcanization and vulcanisates obtainable by this process |
| EP2918612A1 (en) | 2014-03-10 | 2015-09-16 | LANXESS Deutschland GmbH | Hydrogenated nitrile rubber containing aminomethyl groups, method for producing the same, vulcanizable compositions containing hydrogenated nitrile rubber containing aminomethyl groups, method for their vulcanization and vulcanizates obtainable by this method |
| WO2016174203A1 (en) | 2015-04-30 | 2016-11-03 | Arlanxeo Deutschland Gmbh | Use of acrylate rubbers having improved low-temperature properties and good oil resistance for producing vulcanizable mixtures and vulcanized products |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5946272B2 (en) | 1984-11-12 |
| JPS5223152A (en) | 1977-02-21 |
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